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UNIT-3

ELECTROCHEMISTRY CONCEPTS
Electrochemistry may be defined as the branch of chemistry which deals
with the quantitative study of interrelation ship between chemical energy and
electrical energy and inter-conversion of one form into another.relationships
between electrical energy taking place in redox reactions.
A cell is of two types:I.
Galvanic Cell
II.
Electrolytic cell.
In Galvanic cell the chemical energy of a spontaneous redox reaction is
converted into electrical work.
In Electrolytic cell electrical energy is used to carry out a non-spontaneous redox
reaction.
The Standard Electrode Potential for any electrode dipped in an appropriate
solution is defined with respect to standard electrode potential of hydrogen
electrode taken as zero. The standard potential of the cell can be obtained by
taking the difference of the standard potentials of cathode and anode.
E0cell = E0cathode-E0anode
The standard potential of the cells are related of standard Gibbs energy.
∆rG=-nFE0cell
The standard potential of the cells is related to equilibrium constant.
∆rG= -RTink
Concentration dependence of the potentials of the electrodes and the cells are
given by Nernst equation.
aA+bB ne-→ cC + dD
Nernst equation can be written as
Ecell = E0 cell-RT ln[C]c[D]d
nF [A]a[B]b
The conductivity, K of an electrolytic solution depends on the concentration of the
electrolyte, nature of solvent and temperature.
Molar Conductivity, ∆m, is defined by K/C where C is the concentration in Mol L-1
∆M= k*1000
m

the unit of molar conductivity is Ω -1 cm2 mol-1. Molar conductivity of an electrolyte increases with increase in temperature. Concentration of solution in two half cells. (It is not possible to measure single electrode potential because the half cell containing single electrode cannot exist independently.) 3. Emf of a cell depends on following factora. Faraday’s laws of Electrolysis I. Conductivity decrease but molar conductivity increases with decrease in concentration. as charge cannot flow on its own in a single electrode. Name the factor on which emf of a cell depends:Ans. b. c. The amount of chemical reaction which occurs at any electrode during electrolysis by a current is proportional to the quantity of electricity passed through the electrolyte. Corrosion of metals is an electrochemical phenomenon In corrosion metal is oxidized by loss of electrons to oxygen and formation of oxides. Nature of reactants. Kohlrausch law of independent migration of ions. The amount of different substances liberated by the same quantity of electricity passing through the electrolytic solution is proportional to their chemical equivalent weights. 2. Batteries and full cells are very useful forms of galvanic cells There are mainly two types of batteries. What is the effect of temperature on molar conductivity? Ans. Temperature . The law states that limiting conductivity of an electrolyte can be represented as the sum of the individual contribution to the anion and cation of the electrolyte. II. Why is it not possible to measure single electrode potential? Ans. It increases slowly with decrease in concentration for strong electrolyte while the increase is very dilute solutions. Anode (Oxidation): 2Fe(s) →2Fe2+ + 4eCathode (Reduction): O2(g) + 4H+(aq) + 4e-→2H2O Atmospheric Oxidation: 2Fe2+(aq) + 2H2O(l) + 1/2O2(g)→Fe2O3(s) + 4H+(aq) QUESTION CARRING 1 MARK 1.

What is the EMF of the cell when the cell reaction attains equilibrium? Ans. Write Nernst equation – For the general cell reaction aA+bB→cC+dD Ans. The arrangement of various electrodes in the decreasing or increasing order of their standard reduction potentials is called electrochemical series.303RTlog 1 nF [Mn+] EM n+/M can be increased by a. Calculate emf of the following cell at 298K . Nernst equation is: E0 M n+ /M= EM n+ / M . by increasing the temperature.2. Pressure of gas. How is cell constant calculated from conductance values? Ans. Define electrochemical series. Ans. MnO2 and C 8. Zero 7. Ecell = E0cell-RTln[C]c[[D]d nF [A]a[B]b 6. increase in concentration of Mn+ ions in solution b. QUESTIONS CARRYING TWO MARKS 1. 4. 2.? For the reaction Mn+(aq) + ne-. A paste of NH4Cl. 9. What is the electrolyte used in a dry cell? Ans. Ans. Ions 10. How can you increase the reduction potential of an electrode.d. What flows in the internal circuit of a galvanic cell. What are the units of molar conductivity? ( cm2 ohm-1 mol-1 or Scm2mol-1) 5. Cell constant= specific conductance/ observed conductance.→ M (s) Ans.

34) Cu(s)+ 2FeCl3 (aq) → Cu2(aq) + 2 FeCl2(aq) 4. what is conductivity water .76)-0. in aq.34V Ans. easier to oxidize.10V-0. surrounding it. Br. Oxidation potential of Br-.10V+2 X 0.ions are oxidized to Br2 in preference to H2O.0591V log[Zn2+(aq)] [Cu+(aq)] = 0. Electrolysis of KBr(aq) gives Br2 at anode but KF(aq) does not give F2. 6.0591 V = 1. How are standard electrode potentials measured? 7. hydroxides.02955V = 1.10V + 0. Formula of rust. Oxidation takes place at anode.are in the following order.77V) is more than the reduction potential of E0Cu2/Cu(0.34) is more than the reduction potential E0(Fe2+/Fe) (0. Give reason. Write chemical formula of rust.02955Vlog10-4 10-2 = 1.02955V log 10-2 = 1. 3. What happens when a piece of copper is added to (a) an aq solution of FeSO4(b) an Aq solution of FeCl3? a. Now higher the oxidation Potential.1591V Q 3. Cell reaction is as follows.34V-(-0. Write short notes on reduction and oxidation potentials. H2O is oxidized in preference to F-. b.XH2O 5. Solution of KF.Fe2O.44V). Corrosion is a process of determination of metal as a result of its reaction with air and water. On the other hand. Ans. Define corrosion. Copper will dissolve in an aq solution of FeCl3 because reduction potential E0Fe3+/Fe2+(0. Solution of KBr. H2O.76V E0Cu2+/Cu=+0. It is due to formulation of sulphides. etc. Br->H2O>FTherefore in aq. Zn(s) + Cu2+(aq)→ Zn2+(aq) + Cu(s) N=2 T=298K Ecell=(E0Cu2+/Cu-E0Zn2+/Zn)-0. Nothing will happen when the piece of copper is added to FeSo4 because reduction potential E0 Cu2/Cu(0. oxides. What is cell constant? How it is determined? 8.Zn/Zn2+ (10-4 M) || Cu2+ (10-2M)/Cu Given E0 Zn2+/Zn=-0. carbonates.F. Thus in this case oxidation of H2O at anode gives O2 and no F2 is produced.

3.F POTENTIAL DIFFERENCE 1.e.34 V i. As the cell works.. QUESTION CARRYING THREE MARKS 1. cell stops working after some time. 2.It is difference between 1. Why it is necessary to platinize the electrodes of a conductivity cell before it is used for conductance measurement? 10. 1. write reaction involved in h2-o2 fuel cel. E. 2. E0 Ag+/Ag =+0. Calculate the standard cell potential. it is the maximum voltage obtained 2. it is responsible for steady flow of 3.it is difference of potential electrode potential of two electrodes between electrode in a closed when no current is flowing through circuit. Ans. What is fuel cell.80 V identify the cathode and the anode as the current is drawn from the cell. Write the reaction taking place at the electrodes. Write any three differences between potential difference and e.f.it is not responsible for steady Current. Why mercury cell gives the constant voltage.34 V E0 cell 2+ =+0. 3. Why an electrochemical cell stops working after sometime? The reduction potential of an electrode depends upon the concentration of solution with which it is in contact. 11. for the standard cell Cu(s)/Cu+(aq)|| Ag+(aq)/Ag(s) E0 cell 2+/Cu = +0.M. On the other hand if the concentration is more on the reactant side then it will shift the equilibrium in forward direction.9. Then according to Le chatelier’s principle it will shift the equilibrium in backward direction. iii. Now EMF of cell is E0 cell= E0 cathode – E0 anode A decrease in E0 cathode and a corresponding increase in E0 anode wil mean that EMF of the cell will decrease and will ultimately become zero i. When cell works concentration in anodic compartment in cathodic compartment decrease and hence E0 cathode will decrease.it is less than maximum voltage From a cell.m. Obtained from a cell. ii. Flow of current. circuit.From the cell representation . the concentration of reactants decrease.

Why absolute value of reduction potential of electrode cannot be determined? 6.of Cu2+(E0Cu2+/C I. 3.331 gm 4.Ag/Ag+ electrode is cathode and Cu/Cu+ electrode is anode .34V) = +0.5 = 71 gmol-1 X 105 C of charge produce chlorine = 71g 1. Write the equation showing the effect of concentration on the electrode potential. What is understood by a normal hydrogen electrode? Give its significance.76V) is less than the standard reduction potentialof Cu2+ (E0Cu2+/Cu=+0.34V = 0.80V-0.76V) .→Cl2(g) + 2e2 mole 1mol Q= nf Q= 2 x 96500 C/mol= 1. At anode : Cu(s)→ Cu2+ ( aq )+2e-→Ag(s) E0 cell = E0 cathode – E0 anode = E0 Ag+/Ag – E0 Cu2+ /Cu = +. Zn can displace copper from copper sulphate solution.80V Ans.02 A X (15 X 60)sec = 900C Molar mass of Cl2 = 2 X 35. 1.93 X 105 C of charge produce chlorine = 71gm 900 C of charge produce chlorine 71 X 900 1. Since standard reduction potential of Zn2+(E0Zn2+/Zn = -0.80 V – (+0. A metal having lower reduction potential can displace a metal having higher reduction potential from solution of its salt.93 x 105C Quantity of electricity used = IT = 1. .46V 2. How many grams of chlorine can be produced by the electrolysis of matters NaCl with a current of 1. Thus.93 X 105 = 0. E0Zn2+/Zn= -0.34V.34V). Given E0 Cu2+/Cu = +0.02 A for 15 min? 2NaCl(l) →2Na+(l)+2Cl-(l) 2 Cl. Can we store copper sulphate in (i)Zinc vessel (ii) Silver vessel? Give reasons. E0Ag+/Ag = +0. Define electrode potential. 5. CuSo4 solution can be stored in silver vessel.

Corrosion of motor cars is of greater problem in winter when salts are spread on roads to melt ice and snow.? What is the effect of temperature on electrolytic conduction? 4. QUESTIONS CARRYING 5 MARKS 1. What is the use of Platinum foil in the hydrogen electrode? A: It is used for inflow and outflow of electrons. Comment on this statement. Why? 4. Derive the relationship between Gibb’s free energy change and the cell potential. 2.34 Volt) Ans: No it is not safe because reacts with AgNO3 Solution ( Emf will be positive. E0 Cu+/ Cu = 0. Why is Li best reducing agent where as Fluorine is best oxidizing agent ? .Onsagar equation? Ans:. Explain the term electrolysis.) 5. How Nernst equation can be applied in the calculation of equilibrium constant of any cell reaction. Describe normal hydrogen electrode and its applications. 3. What do you understand by ‘electrolytic conduction’? what are the factors on which electrolyte conduction depends. HOT QUESTIONS 1 Mark questions:1. a strong electrolyte shows deviations from Debye-Huckle. The cell reaction as written is spontaneous if the overall EMF of the cell is positive. Is it safe to stir AgNO3 solution with copper spoon? (E0 Ag+/ Ag = 0. 8.? 9. Why is it necessary to use salt bridge in A galvanic cell? Ans: To complete inner circuit and to maintain electrical neutrality of the solution. Discuss briefly the electrolysis of (i) molten NaCl (ii) aqueous sodium chloride solution (iii) molten lead bromide (iv) water.7.Because interionic forces of attractions are large. Why in a concentrated solution. How is electrolytic conductance measured experimentally? 5. 2 mark questions:1.80 Volt. state and explain Faraday’s laws of electrolysis. What is Electrochemical equivalent? 3. 2.

What is the current efficiency ? What are the reactions occurring at anode and cathode ? . What is the molarity of SO4 -2 in the resulting solution and what should be the mass of Zn rod after cleaning and drying ? 5. 5.Explain. Calculate theconcentration of the H+ ions at the positive electrode. Equilibrium constant is related to Eθ cell but not to Ecell. explain. 3.118 V. 7. Why sodium metal is not obtained at cathode when aq NaCl is electrolysed with Pt electrodes but obtained when molten NaCl is electrolysed ? 2 4. ‘ Corrosion is an electrochemical phenomenan’.03V. The emf of the cell is 0. 1 mol KCl dissolved in 500cc of the solution. After certain time interval. the molarity of Cu2+ was found to be 0. Which cell is generally used in hearing aids?Name the material of the anode. Crude copper containing Fe and Ag as contaminations was subjected to electro refining by using a current of 175 A for 6. 6 .8 M. 3/ 5 mark questions:1.1 M aq solution of zinc sulphate which is 95 % dissociated at this concentration. 3 9. 4. What do you mean by ( i) negative standard electrode potential and (ii) positive standard electrode potential ? 2. Write the reactions involved.2. Iron does not rust even if Zinc coating is broken in agalvanised iron pipe but rusting occurs much faster if tin coating over iron is broken. cathode and the electrolyte. H2/ H2SO4.260 g. iron and silver in crude copper. The mass of anode was found to decrease by 22. if its electrode potential is0. Explain. Which will have greater molar conductivity and why? Sol A. Calculate the pH of following cell: Pt.0. What will be the electrode potential of the electrode given that EθZn2+/Zn= .76 V. Zn rod weighing 25 g was kept in 100 mL of 1M copper sulphate solution.434 min. 3. while that of cathode was increased by 22. when Hydrogen gas is bubbled at 1 atm pressure ? 3 10 Electrolysis of the solution of MnSO4 in aq sulphuric acid is a method for the preparation of MnO2 as per the chemical reaction Mn2+ + 2H2O → MnO2 + 2H+ + H2 Passing a current of 27 A for 24 Hrs gives 1 kg of MnO2. 1mol KCl dissolved in 200cc of the solution or Sol B. 8 Zinc electrode is constituted at 298 K by placing Zn rod in 0.011 g. At what pH will hydrogen electrode at 298 K show an electrode potential of -0. Estimate the % of copper. A cell contains two hydrogen electrodes.118 V at 298 K. The negative electrode is in contact witha solution of 10-5 M H+ ions.

403 v E0 Zn++/Zn= -0.763 v Antilog 12.What do you mean by kohlrauch’s law: from the following molar conductivities at infinite dilution ∆m∞ Ba(OH)2 =457.Alpha Mathematics Institute Electrochemistry Q 1.8 Ω-1 cm2 mol-1 Calculate ∆m∞ for NH4OH Q2. electrode (b). Solution of h2So4 with Pt.6 Ω-1 cm2 mol-1 ∆m∞ NH4Cl= 129.4ono.6 Ω-1 cm2 mol-1 ∆m∞ Ba Cl2 = 240.com . An aqueous solution of AgNO3 with silver electrode For more important question's visit : www. Calculate the equilibrium constant for the reaction Zn + Cd2+ Zn2+ +Cd If E0 Cd++/Cd =-.1827 Q3. Predict the products of electrolyzing of the following (a) a dil.